High molecular weight aromatic-aliphatic ordered copolyamides

ABSTRACT

High molecular weight aromatic-aliphatic ordered copolyamides consisting essentially of repeating structural units corresponding to the formula   WHEREIN X and Y are individually selected positive integers and the sum of X+Y is an integer within the range of 4 to 24, inclusive, Z is an integer from 2 to 12, inclusive, and each R is individually selected from the group consisting of hydrogen and a monovalent radical replacement for hydrogen on nuclear carbon which is nonreactive in polyamidation reactions, are prepared. These copolyamides are useful in the preparation of shaped articles (e.g., fibers and films).

United States Patent [72] Inventors Veronika Foldi Wilmington, Del.;Joseph C. Shivers, West Chester, Pa. [21] Appl. No. 876,988 [22] FiledNov. 14, 1969 [45] Patented Nov. 23, 1971 [73] Assignee E. l. du Pont deNemours and Company Wilmington, Del.

[54] HIGH MOLECULAR WEIGHT AROMATIC- ALIPHATIC ORDERED COPOLYAMIDES 13Claims, No Drawings [52] US. Cl 260/78,

[SI] Int. Cl C08g 20/20 [50] Field of Search 260/78 A; 264/210, DIG. 6l

[56] References Cited UNITED STATES PATENTS 3,296,213 1/1967 Preston260/78 Primary Examiner-William H. Short Assistant Examiner-HowardSchain Attorney-Eugene Berman ABSTRACT: High molecular weightaromatic-aliphatic ordered copolyamides consisting essentially ofrepeating structural units corresponding to the formula LL 4 1 LL Q L 1L L l l 1 HQ M- DESCRIPTION OF THE PRIOR ART Ordered polyamides andcopolyamides having both aromatic and aliphatic segments are describedin Detoro US. Pat. No. 3,206,439 and in Preston US. Pat. No. 3,296,2l3.Aromatic-aliphatic polyamides are also shown in Wheatley et al. US. Pat.No. 2,688,0li and in Huffman et al. US. Pat. No. 3.203.933.

SUMMARY OF THE/INVENTION This invention provides filmand fiber-formingordered copolyamides consisting essentially of repeating structuralunits corresponding to the formula wherein X and Y are individuallyselected positive integers Shaped articles prepared from theabove-described copolyamides, such as films and high strength fibers,are also comprehended by this invention. High level tensile propertiesare imparted to the fibers by a post-extrusion heat treatment.

V The combination of tenacity and modulus properties which characterizethe copolyamides of this invention are particularly unusual forcopolyamides having aliphatic segments.

The copolyamides of this invention exhibit inherentviscosities of atleast about 0.8, preferably above I. when measured by proceduressubsequently described.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Copolyamides The orderedcopolyamides of this invention may be prepared by low temperaturesolution polymerization techniques wherein aromatic diamins containingpreformed amide linkages are caused to react with amide-formingderivatives of suitable aliphatic dibasic acids. The'se aromaticmacrodiamines, preferably formed in situ prior to the addition of thedibasic acid comonomer, correspond to the formula:

wherein X, Y, and R have the significance previously recited.

m'ethanesulfonate,

The diamine of formula (II) may be formed in situ by the reactionbetween p-phenylenediamine and/or ring-substituted derivatives thereofand suitable 4-aminobenzoic acid derivatives and/or ring substitutedderivatives thereof. Preferred among the aminobenzoic acid derivativesare benzoyl hydrohalides of the formula wherein Q and 0' representhalogen. either or both-preferably being chlorine or bromine. andR hasthe significance set forth hereinbefore. The singularly preferredformula (III) reactant is 4-'aminobenzoyl chloride hydrochloride, withother useful formula (III) reactants being 4-aminobenzoyl chloridehydrobromide, 4-ami'nobe'nzoyl bromide hydrochloride, 4- ami'riobenzoylbromide hydrobromide, 3-fluoro-4-aminobenzoyl chloride hydrochlorideZ-chloro aminobenzoyl chloride hydrochloride 3-carbomethoxy aminobenzoylchloride'hydrochloride 3-bromo-amin'obenzoyl chloride hydrochloride3-iodo-aminobenzoyl chloride hydrochloride 2-fluoro-aminobenzoylchloride hydrochloride 2,3-dirnethyl-aminobenzoyl chloride'hydrochloride 3-ethyl-aminobenz'oyl chloride hydrochlorideZ-nitro-aminobenzoyl chloride'hydrochloride 3-ethoXy-aminobenzoylchloride-hydrochloride 2-ethox'y 5-nitro-aminobenzoyl chloridehydrochloride 2-propoxy-aminobenzoyl chloride hydrochloride2-isobutosy-aminobenzoyl chloride hydrochloride2-sec.butoxy-aminobenzoyl chloride hydrochloride 3-propoxy-aminobenzoylchloride hydrochloride 3-isopropoxy-aminobenzoyl chloride hydrochloride3-butoxy-aminobenzoyl chloride hydrochloride 2-methylthio-aminobenzoylchloride hydrochloride 2-ethylthio-aminobenzoyl chloride hydrochloride2,5-dimethyl aminobenzoyl chloride-hydrochloride2-ethysulfonyl-aminobenzoyl chloride hydrochloride2-dimethylsulfamoyl-aminobenzoylchloride hydrochloride Other4'-aminobenzoic acid derivatives not conforming to formula (III) arealso useful, e.g., 4-aminobenzoyl chloride 4-aminobenzoyl chloridebenzenesulfonatc, and 4-aminobenzoyl bromide ethanesulfonate Inpreparing a formula (II) diamine, (X+Y) moles of the aminobenzoic acidderivative or derivatives are used for each mole of p-phenylenediamineor derivatives employed.

p'-Oriented aromatic diamines which can be caused to react with4-aminobenzoic acid and derivatives thereof according to this inventioncorrespond to the formula:

(III) wherein R has the significance defined hereinbefore. Usefulfonnula (IV) diamines include p-phenylencdiamine. 2.5- toluenediamin'e,2-nitro-p-phenylenediamine. 2.3-dichloropphenylenediamine,2,5-dichloro-p-phenylenediamine, 2,6- dichloro-p-phenylenediamine,2-bromo-p-phenylenediamine. and 2,5-dibromo-p-phenylenediamine.

Dicarboxylic acids whose amide-forming derivatives may be employed toprepare the copolyamides of this invention correspond to the formula (V)"00C (CH2): COOH wherein Z has the significance set forth hereinbefore.Useful formula (V) acids are succinic. glutaric, adipic, pimelic,suberic, azelaic, sebacic. undecanedioic, dodecanedioic. tridecanedioic,and tetradecanedioic. These dicarboxyclic acids are convenientlyemployed in the form of their dihalides which are readily prepared bywell-known methods. The diacid chloride is usually preferred.

The formula (l) copolyamides of this invention which are especiallypreferred for fiber preparation are those wherein (l) the sum ofX+Y is 8and Z is 4 and (2) the sum of X+Y is 12 and Z is 4. Other preferredcopolyamides are those wherein the sum of X+Y is 23 and Z is 4, andwherein the sum of X+Y is 12 and Z is 5.

Polymerization Conditions in the low temperature solution polymerizationprocess. i.e., under 50 C., and preferably from to 30 C.. which providesthe novel polymers of this invention, a solvent or a mixture of solventsselected from the group consisting of hexamethylphosphoramide.N,N-dimethylacetamide. N,N- dimethylpropionamide. N-methylpyrrolidone-Z.and N.N,N'. N'-tetramethylurea is preferably employed.

The preparation and isolation of a formula (I) copolyamide may becarried out by first placing the desired quantity of the aminobenzoicacid derivative(s) in a thoroughly dried reaction vessel equipped with astirrer. nitrogen inlet, and drying tube; the reactant may be moistenedwith a small amount of appropriate liquid, e.g.. tetrahydrofuran. Tothis slowly stirred mixture. swept with a stream of dry nitrogen, israpidly added an appropriate amount of formula (IV) diamine(s) dissolvedin a quantity of suitable solvent (e.g., hexamethylphosphoramide)sufficient to give a final concentration of copolyamide of formula (I)within the range of about 6 to 12 weight percent. The rate of stirringis increased; after stirring is continued for about 0.5 hour atautogenous temperature, the stirred reaction mixture is cooled (e.g., onan ice bath) for about 0.5 hour. The acid halide(s) of formula (V).which may be dissolved inan appropriate solvent (e.g.. is then added tothe cold solution of the macrodiamine of formula (II Stirring andcooling are continued for about O.5-l hour, after which the reactionmixture is permitted to stand overnight at room temperature. Dependingupon the composition and concentration of the copolyamide of formula(I). the reaction mixture obtained may be a stiff gel. a thick paste. ora solution. The reaction mixture may be combined with water. thecopolymer isolated. washed (e.g.. in a blender with water and alcohol).and dried in an oven prior to being redissolved for further processing.Yields are usually quantitative.

CHain terminators to limit the molecular weight of the copolyamides ofthis invention may be used if desired. These may be added with theformula (V) reactant. Among the suitable chain terminators are compoundswhich can react with acid chloride groups such as ammonia. monoaminese.g., ethylamine. dimethylamine. diethylamine, butylamine. dibutylamine,cyclohexylamine, aniline, etc. compounds containing a singleamide-forming group such as N.N- diethylethylenediamine. hydroxyliccompounds such as methyl alcohol, ethyl alcohol. isopropyl alcohol.phenol, etc.. and compounds which can react with amine groups such asother acid chlorides (e.g.. acetyl chloride). acid anhydrides (e.g.,acetic anhydride. phthalic anhydride). and isocyanates.

(e.g., phenylisocyanate, ethyl isocyanate. etc.

Lithium chloride advantageously may be present in the polymerizationmixture since this salt may assist in maintaining a fiuid. stirrable,mixture during polymerization. The salt may be added at the beginning ofthe reaction, during its course or may be formed in situ. At least 4weight percent (based on the combined weight of all ingredients) of saltis suitable. For the preparation of spinning dopes by dissolution ofisolated polymers as well as for the preparation of dopes via in situpolymer formation and fiber extrusion. a lithium chloride range of about4 to about 6 weight percent is preferred.

When. with'proper choice of comonomers used in the polymerization.hydrogen chloride is generated as a byproduct of the'polymerizationreaction. the salt may also be provided by forming it in situ byneutralizing the hydrogen chloride with a base selected from the groupconsisting of lithium carbonate. lithium oxide. lithium hydroxide(includes monohydrate), and lithium hydride. or mixtures thereof. Theneutralization is especially preferred in embodiments of this inventionwherein the reaction mixture may be utilized directly for the formationof shaped articles of the copolymer. It will be recognized that anunneutralized acidic byproduct. e.g.. hydrogen chloride. may causesignificant corrosion problems in conventional processing equipment.such as in the spinnerets used for fiber preparation. g

If the choice of comonomers employed does not lead to the production ofhydrogen chloride during the polymerization reaction. the acidicbyproduct of the polymerization may still be neutralized with theaforementioned bases. and the lithium chloride added to thepolymerization mixture to assist in maintaining a fluid composition.Under the polymerization conditions useful in obtaining the copolymersdescribed herein. the neutralization of the reaction mixture with thelithium base may produce an insoluble salt in the reaction mixture.lnsoluble precipitates which may result by virtue of the choice ofcomonomers and neutralizing agent should be removed e.g. by filtration)before the polymerization mixture is extruded into fibers or cast intofilms.

Dope and Shaped Article Preparation As previously noted. shaped articlessuch as fibers and films may be formed from dopes of the copolyamides ofthis invention.

The formula (l) copolyamides which are isolated in bulk form may beconverted into shaped articles by first incorporating them into dopeswhich are then extruded into fibers. cast into films. etc. These dopesare essentially comprised of the copolyamide; a solvent or mixture ofsolvents selected from the group consisting of N.N-dimethylacetamide.N.N- dimethylpropionamide. Nmethyl-pyrrolidone-2. hexamethylphosphoramide. N.N.N', N'-tetramethylurea admixed with lithiumchloride; or strong acids such as concentrated sulfuric acid. ClSO H.and HF. In general. the maximum copolymer content possible in the dopedecreases as the inherent viscosity of the copolyamide increases.Preferably. isolated bulk polymer is finely divided (e.g.. comminuted byball .milling) prior to dope preparation. Dopes may contain from about 5to about l2 weight percent of the copolyamide, from about 4 to about 6weight percent of lithium chloride. and the balance is one or more ofthe appropriate solvents previously noted.

Dopes useful for extrusion into fibers may be prepared by stirring asuspension of copolyamide. solvent. and salt on a steam both untileither a solution or a clear gel results. In the latter case, the gelmay be cooled in ice water to obtain a free flowing solution. Additionof more copolymer or solvent to obtain a desirable dope may benecessary.

The dopes prepared as described above may be extruded into fibers byconventional wetand dry-spinning techniques and equipment. Inwet-spinning. an appropriately prepared dope. whose temperature may varyfrom 5 to about 50 C.. is extruded into a suitable coagulating bath.e.g.. a water bath maintained between about 10 to about 40 C. Otheruseful coagulants include ethylene glycol. mixtures of water andalcohol. and aqueous salt baths Dry-spinning may be accomplished byextruding the warm dope into a heated current of gas whereby evaporationoccurs and fibers are formed.

After being fonned. the fibers may be passed over a finish applicationroll and wound up on bobbins. Development of maximum levels of filamentand yarn properties is assisted by soaking the bobbins in water ormixtures of water and water miscible inert organic liquids (e.g..acetone. ethyl alcohol. N.N-dimethylacetamide) to remove residualsolvent and salt. after which the fibers are dried. Removal of the saltand solvent may also be accomplished by running the fiber or yarnthrough aqueous baths on the run. by flushing the bobbins with water asthe yarn is formed. and by soaking or washing skeins rather thanbobbins, of yarn.

The dopes comprising the copolyamides of this invention may be formedinto strong self-supporting films by conventional wet-extrusion methods.The dopes may also be used for fibrid preparation, useful for paperpreparation, via the precipitation procedures described in Morgan US.Pat. No. 2,999,788.

It will be understood that the usual additives such as dyes, fillers, UVstabilizers, antioxidants, etc., can be incorporated in with thecopolyamides for the purposes intended prior to shaped articlepreparation.

The properties of fibers prepared from the copolyamides of thisinvention are enhanced by a post-preparative heat treatment. Forexample, the tensile properties of as-extruding fibers can be increasedby subjecting the fibers to a heat treatment wherein the fibers are keptunder tension or are drawn slightly. Drawing may vary from essentiallynone to as much as 50 percent. Hot air ovens, hot pins, hot slots, hotplates, and liquid heating baths are useful for such treatments. Thetensile properties of as-extruded fibers preferably are enhanced byapplying heat in the temperature range of between about 300 to 600 C.,preferably between about 400 to 550 C., to the fib rsu reb snaa telQmslsin. anjnq ta mosphere, preferably a nitrogen atmosphere whiledrawing the fibers from about 0 to 50 percent. The apparatus in whichthe copolyamide fibers exemplified herein are heated while under tensionor being drawn is described hereinafter.

The high tenacity, high modulus copolyamide fibers of this invention,prepared by the means described above, exhibit tenacity values in excessof about 3 g.p.d., initial modulus values in excess of about 275 g.p.d.,and orientation angles less than about 35. Preferably, these fibersexhibit tenacity values in excess of about 4.5 g.p.d., initial modulusvalues in excess of about 400 g.p.d., and orientation angles less thanabout 25.

The copolyamide fibers of this invention are useful for tire cords andin reinforced plastic laminates because of their high initial modulus,strength, and thennal stability. Specific end uses for laminates mayinclude skis, bows, fishing rods, and golf club shafts.

MEASUREMENTS AND TESTS Inherent Viscosity: Inherent viscosity (ninh) isdefined by the following equation:

, inh

wherein (nrel) represents the relative viscosity and C represents aconcentration of 0.5 gram of the polymer in 100 ml. of solvent, unlessotherwise noted. The relative viscosity (nrel) is determined by dividingthe flow time in a capillary viscometer of a dilute solution of thepolymer by the fiow time for the pure solvent. The dilute solutions usedherein for determining (nrel) are of the concentration expressed by C,above; flow times are determined at 30 C with concentrated(95-98percent) sulfuric acid as a solvent.

Tensile Properties: Fiber properties of tenacity, elongation, andinitial modulus are coded as TIE/Mi and are reported in .theirconventional units. Denier is coded as Den. The boiling off treatment offibers prior to physical testing consists of boiling the fibers 30minutes in 0.1 percent aqueous sodium lauryl sulfate, rinsing, drying at40 C. for l hours, and conditioning at 21 C. and 65 percent r.h. for 16hours. Tensile properties are determined on filament samples measuring 1inch (2.54 cm.) in length between the jaws of an lnstron tester (productof the lnstron Engineering Corp., Canton. Mass), and which are subjectedtherein to a load sufficient to cause elongation to occur at the rate ofl0 percent per minute measured at 2l C. and 65 percent r.h.

Heat Treatment:

Unless otherwise stated in the following examples, the postextrusionheat treatment applied to the fibers and yarns of this inventioncomprises passing them through a heated, nitrogenfilled inner stainlesssteel tube 32 in. (81.3 cm.) X 0.3125 in. (7.94 mm.) (l.D.) mountedconcentrically in a second tube 1.06 in. (2.69 cm.) O.D.], the wholeassembly being centered in a 12 in. (30.48 cm.) electric furnace.Nitrogen gas enters through 2 nipples in the outer tube located 10 in.(25.4 cm.) out from either side of the center of the tube, such that theincoming nitrogen passes through the annular space between the twotubes. The nitrogen passes from the annular space into the inner tubethrough a small hole located in the wall of the inner tube to its centerand thence out the ends of the inner tube at such a rate as to changethe atmosphere in the 12 in. (30.48 cm.) heated cone of the inner tubeat least once a minute. The outer ends of the device which protrude fromthe furnace are wrapped with asbestos fiber and glass tape to withinabout 2 in. (5.98 cm.) of each end. The temperature of the furnace iscontrolled by a thermocouple brazed to the center of the outside wall ofthe outer tube and connected to a Minneapolis-Honeywell Pyrovane"controller. The heated tube has a temperature profile with the maximumtemperature in the center region. The nominal heat-treating temperatureis determined by a thermocouple brazed to the outer central surface ofthe inner tube. In passing fibers through the tube, guides are used tokeep the fiber centered and out of contact with the tube walls.

Orientation Angle:

The orientation angle of the fiber (filament) is determined by thegeneral method described in Krimm and Tobolsky, Textile ResearchJournal, Vol. 21, pp. 805-22 (ll). A wide angle X-ray diffractionpattern (transmission pattern) for the fiber is made using a Warhuspinhole camera. The camera consists of a collimator tube 3 in. (7.6 cm.)long with two lead (Pb) pinholes 25 mils (0.0635 cm.) in diameter ateach end, with a sample-to-film distance of 5 cm.; a vacuum is createdin the camera during the exposure. The radiation is generated by PhilipsX-ray unit (Catalog No. 12045) with a copper finefocus diffraction tube(Catalog No. 32 l 72) and a nickel betafilter; the unit is operated at40 kv. and I6 ma. A fiber-sample holder 20 mils (0.051 cm.) thick isfilled with the sample; all the filaments that are in the X-ray beam arekept parallel. The difi'racu'on pattern is recorded on Kodak No-Screenmedical X-ray film (NS-54T) or equivalent. The film is exposed for asufficient time to obtain a pattern which is considered acceptable byconventional standards (e.g., a pattern in which the diffraction spot tobe measured has a sufficient photographic density, e.g., between 0.2 andL0, to be accurately readable). Generally, an exposure time of about 45minutes is suitable; however, a lesser exposure time may be suitable,and even desirable, for highly crystalline and oriented samples toobtain a more accurately readable pattern. The exposed film is processedat a temperature of 68i2 F. in Du Pont Cronex X- ray developer for 3min., in a stop bath (30 ml. of glacial acetic acid in l gal. [3,785l.]of distilled water) for 15 sec.. and in General Electric SupermixX-ray fixer and hardener solution for 10 min. The film is washed inrunning water for 0.5 hr. and is dried.

The arc length in degrees at the half-miximum intensity (anglesubtending points of 50 percent of maximum intensity) of the principalequatorial spot is measured and taken as the orientation angle of thesample.

The method used to determine orientation angles in the filaments of theinstant invention employs an improved version of the flying-spot"densitometer described by Owens and Statton in Acta Cryst." (I957), l0,560-562. The equipment used is similar to that described by Owens andStatton in their FIG. 1, with the following difierences:

l. The Sola Constant Voltage Transformer No. 80808 is replaced bycatalog No. 23-2412, and this unit is connected only in series betweenthe master switch of the 500 Volt Regulated Supply.

2. The Dumont No. 304 A Display Oscilloscope and the adjacentCalibrating Signal Generator are replaced by a Tektronix 532 DisplayOscilloscope combined with a Tektronix Type 53/54 K Preamplifier. Thecombined units are connected in series only between the Main Switch andthe Photomultiplier.

3. The Flying Spot Oscilloscope (Dumont No. 304 A) and its Cathode-RayTube are replaced by a Tektronix 536 Oscilloscope having a 536 PCathode-Ray Tube.

4. The 500 Volt Regulated Supply is connected to the Photomultiplier andalso to the Circle Generator (a type of device designated by Owens andStatton as a Scanning Frequency Generator).

5. The Circle Generator is connected at one point through a TektronixType 53/54 K Horizontal Preamplifier and at a second point through aline-circle switch and a Tektronix Type 53/54 K Vertical Preamplifier tothe Tektronix 536 Oscilloscope.

Operation of this device follows the instructions given by Owens andStatton, except that the calibration with a square wave from a signalgenerator is not necessary. As described in the article, a metal blockconveniently establishes the infinite density level of the displaydiagram. A clear portion of the film provides a reference for zerodensity.

As noted by the authors, the "flying-spot" densitometer provides a rapidmeasure of the orientation angle and the photographic density (opticaldensity).

EXAMPLES unless otherwise indicated.

EXAMPLE 1 This example illustrates the preparation of 1 a formula (1)polyamide wherein X+Y=4 and Z=2, and (2) fibers thereof.

p-Aminobenzoyl chloride hydrochloride (15.36 g., 0.08 mole) and ml. oftetrahydrofuran (THF) are placed in a resin kettle fitted with aneggbeater type stirrer. To this is added p-phenylenediamine (2.16 g.,0.02 mole) in 100 ml. of hexamethylphosphoramide (HMPA a 10 ml. rinse ofHMPA is added to the kettle, also. After the combined ingredients arestirred for 0.5 hr., the solution is cooled in an icebath and succinylchloride (3.18 g., 0.02 mole) in 20 ml. of THF is added to the kettle.followed by two 5 ml. rinses of THF. The reaction mixture is stirred inthe cold for 1 hr., then stirred overnight at room temperature. Theresulting thick white paste is combined with water. The precipitatedpolymer is then collected, washed (blender) five times with water andonce with 28 a1- cohol, and dried at 80 C. in a vacuum oven; ninh=1.29.

A spinning dope is prepared by combining 9 g. of the abovepreparedpolyamide with 70 g. of a mixture of N,N-dimethylacetamide/LiCl (95/5,wt./wt.; this mixture is hereinafter identified as the solventmixture"). The dope (containing 11.4 percent by weight polymer) isextruded through a 20- hole spinneret (each hole of 0.003 inch diameter)into a water bath (maintained at 28 C.) and coagulated into filamentswhich are wound up at 16 ft./min. After the resultant yarn is extractedwith water and dried, the filaments thereof exhibit the followingtensile properties: TIE/Mi: 1.46/33/71. After the yarn has been drawn1.3X at 400 C., the filaments thereof exhibit the following tensileproperties: llE/M: 5.6/1.5/476; the filaments are highly crystalline;O.A.=

EXAMPLE 2 This example illustrates preparation of (1) a formula (1)polyamide wherein X+Y =4 and Z=4, and (2) fibers thereof.

The procedure of example 1, above, is repeated with the exception thatadipyl chloride (3.66 g., 0.02 mole) is used instead of succinylchloride. Also, only a single 5 ml. THF rinse is employed. For theovendried product, ninh =1.59.

A spinning dope is prepared by combining 1 1 g. of the above-preparedpolyamide with g. of solvent mixture on a steam bath, with stirring. Thedope (containing 9.5 percent solids) is extruded as in example 1 into awater bath maintained at 22 C. and coagulated into filaments which arewound up at 23 ft./min. After the resultant yarn is washed and dried asin example 1, the filaments thereof exhibit the following tensileproperties: T/El Mi: 1.5/23/76. After the asextruded yarn has been drawn1.05X at 500 C., the filaments thereof exhibit the following tensileproperties: T/E/ Mi: 8.1/1.6/571; O.A.=13.

EXAMPLE 3 1 This example illustrates preparation of (1) a formula (I)polyamide wherein X+Y =8 and Z =2. and (2) fibers thereof.

p-Aminobenzoyl chloride hydrochloride (30.72 g., 0.16 mole) and 20 m1.of THF are placed in a resin kettle as in example 1. The procedure ofexample 1, above is then followed with the exception that thep-phenylenediamine is dissolved in 200 ml. of HMPA. For the oven driedproduct, ninh =1.28.

A spinning dope is prepared by combining 7.5 g. of the above-preparedpolyamide with 105 g. of the solvent mixture on a steam bath, withstirring. The dope (containing 6.6 percent solids) is extruded as inexample 1 into a water bath (maintained at ambient temperature) andcoagulated into filaments which are wound up at 62 ftJmin. After theresultant yarn is extracted with water and dried, the filaments thereofEXAMPLE 4 This example illustrates preparation of (1) a formula (1)polyamide wherein X+Y =8 and Z =4, and (2) fibers thereof.

The procedure of example 3, above, is repeated with the exceptions thatthe diacid chloride employed is adipyl chloride (3.66 g., 0.02 mole) andthat stirring with cooling is per formed for 0.5 hr. just prior topermitting the reaction mixture to stand overnight. For the ovendriedproduct. ninh =1.69.

A free-flowing spinning dope is prepared by first combining 10 g. of theabove-prepared polyamide with 90 g. of solvent mixture; the combinedingredients are then maintained on a steam bath for 2 hrs. The dope(containing 10 percent by weight polymer) is extruded through aspinneret (similar to that in example 1) into a water bath maintained at21 and coagulated into filaments which are wound up at 13.5 fi./m in.After the resultant yarn is extracted with water and dried. thefilaments thereof exhibit the following tensile properties: T/E/Mi:1.7/40/73. After the yarn has been drawn 1.2X at 536 C., the filamentsthereof exhibit the following tensile properties: T/E/Mi: 9.1/1 .3/737;O.A.=9.

EXAMPLE 5 This example illustrates preparation of a formula (1)polyamide wherein X+Y =8 and Z =10.

The procedure of example 1, above, is repeated with the exceptions thatonly half the previous amount of p-phenylenediamine is employed and thatdodecanedioyl chloride (2.67 g., 0.01 mole) is employed as the diacidchloride. For the ovendried product. ninh =1.39.

EXAMPLE 6 This example illustrates the preparation of 1 a formula (1)polyamide wherein X+Y =12 and 2 =2, and (2) fibers thereof.p-Aminobenzoyl chloride hydrochloride (23.04 g., 0.12 mole) and 20 ml.of THF are placed in a resin kettle. To this is added p-phenylenediamine1.08 g.. 0.01 mole) in m1. of

HMPA; a 20 ml. rinse of HMPA is employed also. The combined ingredientsare stirred for 0.5 hr. The solution is cooled in an icebath andsuccinyl chloride (1.59 g., 0.01 mole) in 10 ml. of THF is then added tothe kettle, followed by two ml. rinses of THF. The reaction mixture isstirred in the cold for about 0.5 hr., after which it is permitted tostand at room temperature overnight. The reaction mixture is thencombined with water to precipitate the polymer which is collected.washed (blender) 4 times with water and once with 28 alalcohol and driedat 100 C. in a vecuum oven; ninh=l.l l.

A spinning dope is prepared by combining l o g. of the above-preparedpolyamide with 90 g. of solvent mixture to form a very viscous clearsolution. An additional 25 g. of solvent mixture are added. The dope(containing 8 percent by weight polymer) is extruded through a spinneretsimilar to that in example 1 into a water bath maintained at 28 C. andcoagulated into filaments which are wound up at 52 ft./min. After theresultant yarn is extracted with water and dried, the filaments thereofexhibit the following tensile properties: TIE/Mi: 1.6/17/82. After theyarn has been drawn 1.3x at 450 C., the filaments thereof exhibit thefollowing tensile properties: TIE/Mi: 4.6/1 .0/494; O.A.=l 3

EXAMPLE 7 This example illustrates the preparation of l a formula (1)polyamide wherein X+Y =12 and 2 =4, and (2) fibers thereof.

p-Aminobenzoyl chloride hydrochloride (23.04 g., 0.12 mole) and 20 ml.of THF are placed in a resin kettle, with stirring. To this is addedp-phenylenediamine 1.08 g., 0.01 mole) in 130 ml. dry HMPA, with rapidstirring. A 20 ml. rinse of l-lMPA is added to the kettle, also. After0.5 hr., a viscous, clear solution results; this is then cooled in icefor an additional 0.5 hr. Adipyl chloride (1.83 g., 0.01 mole) is addedto the kettle, followed by two 5 ml. rinses of THF. The resultingsolution is stirred, with ice bath cooling for 0.5 hr., after which theice bath is removed. In 20 minutes, the reaction mixture forms anunstirrable, clear mass which is permitted to stand overnight at roomtemperature. The reaction mixture is then combined with water toprecipitate the polymer which is collected, washed (blender) 5 timeswith water and once with 2B alcohol, and dried at 80 C. overnight in avacuum oven; ninh=1.6.

A spinning dope is prepared by combining 12 g. of the above-preparedpolyamide with 108 g. of the solvent mixture. The dope ingredients arestirred on a steam bath for 0.5 hr. to form a clear, viscous dope whichis maintained overnight at room temperature. The dope (containingpercent by weight polymer) is centrifuged. It is then extruded through aspinneret similar to that described in example 1 into a water bathmaintained at 1 1 C. and coagulated into filaments which are wound up at25 ft./rnin. After the resultant yarn is extracted for 16 hours indistilled water and dried, the filaments thereof exhibit the followingtensile properties: T/E/Mi: 1.8/29/83. After the yarn has been drawn1.2X at 480 C., the filaments thereof exhibit the following tensileproperties: TIE/Mi; 1071.6/705; ).A.=l1. filaments from yarn which wasdrawn 1.2X at 538 C. exhibit the following tensile properties: TIE/Mi:13/ 1 .7/870; 0.A.= 1 1'.

EXAMPLE 8 This example illustrates the preparation of (1 a formula (1)polyamide wherein X+Y =12 and F10 and (2) fibers thereof.

The procedure of example 7 above, is repeated with the exception thatdodecanedioyl chloride (2.67 g. 0.01 mole) is the diacid chlorideemployed; this is added in 10 ml. of THF and two 5 ml. THF rinses arealso added. After the addition of diacid chloride, the reaction mixtureis permitted to stand overnight at room temperature. The reactionmixture is then combined with water to precipitate the polymer which iscollected, washed (blender) 5 times with water, and dried at 100 C. in avacuum oven; ninh=1.36.

A spinning dope is prepared by combining 10 g. of the above-preparedpolyamide with g. of the solvent mixture. This combination (containing10 percent by weight polymer) is heated on a steam bath for 20 minutes,then is cooled in ice, after which an additional 20 g. of solventmixture are added, with stirring and cooling. The viscous dope iscentrifuged before being extruded through a spinneret (similar to thatin example l) into a water bath maintained at 25 C. and coagulated intofilaments which are wound up at 39 ft./min. After the resultant yarn isextracted in water and dried, the filaments thereof exhibit thefollowing tensile properties: T/E/Mi: 1.7/9.2/104. After the yarn hasbeen drawn 1.1X at 536 C., the filaments thereof exhibit the followingtensile properties:

TIE/Mi: 6.8/1 .8/449; O.A.=l 1.

EXAMPLE 9 This example illustrates the preparation of l) a formula (1)polyamide wherein X+Y =18 and 2 =10, and (2) fibers thereof.

p-Aminobenzoyl chloride hydrochloride (34.56 g., 0.18 mole) and 40 ml.of THF are combined. To this is added pphenylenediamine (1.08 g., 0.01mole) in 150 ml. HMPA; a 50 ml. rinse of HMPA is added, also: After the551E183 ingredients are stirred for 0.5 hr., they are cooled in an icebath (with stirring) and dodecanedioyl chloride (2.67 g., 0.01 mole) in10 ml. of THF is added, followed by 5 ml. rinses of THF. The reactionmixture is stirred in the cold for 5 min., after which it becomesunstirrable. The reaction mixture is then left overnight at roomtemperature. It is then combined with water to precipitate the polymerwhich is collected, washed (blender) 5 times with water and once with 28alcohol, and dried at C. in a vacuum oven under nitrogen; ninh=l.86.

A spinning dope is prepared by combining 8 g. of the abovepreparedpolyamide with 92 g. of solvent mixture. The combined ingredients arefirst stirred on the steam bath for 0.5 hr., after which they are cooledin ice for 1.5 hrs. An additional 14 g. of solvent mixture are thenadded, with stirring and cooling being continued. There is obtained afree-flowing, viscous dope containing 7 percent by weight polymer. Thedope is extruded through a spinneret (similar to that in example 1) intoa water bath maintained at 11 C. and coagulated into filaments which arewound up at 22 ttJmin. After the resultant yarn is extracted with waterovernight and dried in air, the filaments thereof exhibit the followingtensile properties: TIE/Mi: 2.4/30/87. Filament tensile propertiesobserved after the yarn has been drawn under various conditions arerecorded in table 1, below.

TABLE 1 Fllnnwnt properties Orientation n anglov Yarn drawing conditions'I E M1 (dog) 1.2X at 450 C 8. l 2. l 438 ll 1.2x at 480 C 8. i 1. l 484ll 1.1X at 636 C 9. J .l. .3 474 13 1.3Xat536C 9.5 1.8 571 10 EXAMPLE 10This example illustrates the preparation of l a formula (I) polyamidewherein X+Y=23 and 2 4. and (2) fibers thereof.

pAminobenzoyl chloride hydrochloride (44.56 g... 0.23 mole) and 40 ml.of THF are combined in a resin kettle. To this is addedp-phenylenediamine 1.08 g., 0.01 mole) in ml. of HMPA; a 50 ml. rinse ofHMPA is added to the kettle, also. The resulting clear, viscous solutionis stirred at room temperature for 0.5 hr. The solution is then cooledin ice and adipyl chloride 1.83 g., 0.01 mole) in 10 ml. ofTHF is added,followed by two 5 ml. rinses of THF. The ice bath is removed andstirring continued for 10 minutes, after which time the reaction'mixturebecomes unstirrable. After the reaction mixture is permitted to standovernight at room temperature, it is combined with water to precipitatethe polymer which is collected, washed (blender) with water and 23alcohol, and dried at 80 C. in a vacuum oven; ninh=1.72.

A spinning dope is prepared by combining 15 g. of the above-preparedpolyamide with 155 g. of solvent mixture. After the combined ingredientsare warmed on a steam bath for 20 min. and pennitted to stand at roomtemperature 2 hr., a clear, viscous dope containing 8.8 percent byweight polymer is obtained. The dope is permitted to stand overnight atroom temperature, after which it is centrifuged. The dope is extrudedthrough a spinneret (similar to that in example 1 into a water bathmaintained at ll" C. and coagulated into filaments which are wound up at32 ft./min. After the resultant yarn is extracted with water and driedin air, the filaments thereof exhibit the following tensile properties:T/E/Mi: 2.2/25/74. Filament tensile properties observed after the yarnhas been drawn under various conditions are recorded in Table II, below.

This example illustrates the preparation of l) a formula (I) polyamidewherein X+Y =12 and 2 =5, and (2) fibers thereof.

The procedure of example 7, above, is repeated with the exception thatthe first-combined ingredients are stirred for 1 hr. before being cooledin ice. Then, in place of the adipyl chloride. there is added pimeloylchloride (L97 g., 0.0l mole) in 10 ml. of THF, followed by a 5 ml. rinseof THF. The stirred reaction mixture becomes a crumbling gel in aboutmin. and is permitted to stand overnight at room temperature. Thereaction mixture is then combined with water to precipitate the polymerwhich is collected, washed (blender) 4 times with water, once with 28alcohol and once with acetone, and dried overnight in a vacuum oven;ninh=l .75.

A spinning dope is prepared by combining l0 g. of the above-preparedpolyamide with 90 g. of solvent mixture. These ingredients are heated ona steam bath for min., after which they are permitted to cool. Anadditional l0 g. of solvent mixture is added to form at roomtemperature, a fluid spinning dope containing 9.1 percent by weightpolymer. Thedope is extruded through a spinneret (similar to that shownin example I) into a water bath maintained at 28 C. and coagulated intofilaments which are wound up at 40 ft./min. After the resultant yarn isextracted with water and dried, the filaments thereof exhibit thefollowing tensile properties: T/E/Mi: l.8/28/74. After the yarn has beendrawn l.25X at 538 C., the filaments thereof exhibit the followingtensile properties: TIE/Mi: lO/l .8/612; O.A.=l 2What is claimed is:

essentially of repeating structural units corresponding to the wherein585d Y are individually selected positive integers and the sum of X+Y isan integer within the range of 4 to 24, inclusive, Z is an integer from2 to 12, inclusive. and each R is individually selected from the groupconsisting of hydrogen and a monovalent radical replacement for hydrogenon nuclear carbon which is nonreactive in polyamidation reactions; andhaving an inherent viscosity of at least 0.8, measured at 30 C. using asolution containing 0.5 g. of the polymer in 100 ml. of concentrated(-98 percent) sulfuric acid.

2. An aromatic-aliphatic ordered copolyamide as recited in claim 1,wherein R is selected from the group consisting of hydrogen, halogen,lower alkyl. lower alkoxy, cyano. nitro, alkylthio, alkysulfonyl,alkylsulfamoyl, and carboalkoxy.

3. An aromatic-aliphatic ordered copolyamide as recited in claim 1,wherein the sum of X+Y is 8 and Z is 4.

4. An aromatic-aliphatic ordered copolyamide as recited in claim I.wherein the sum ofX+Y is l2 and Z is 4.

5. An aromatic-aliphatic ordered copolyamide as recited in claim I,wherein the sum of X+Y is 23 and Z is 4.

6. An aromatic-aliphatic ordered copolyamide as recited in claim 1,wherein the sum of X+Y is l2 and Z is 5.

7. A shaped article of the aromatic-aliphatic copolyamide recited inclaim 1.

8. A shaped article of claim 7 in film form.

9. A shaped article of claim 7 in fiber form.

10. A fiber of the aromatic-aliphatic copolyamide recited in claim I.having a tenacity value in excess of about 3 g.p.d., initial modulusvalue in excess of about 275 g.p.d.. and an orientation angle less thanabout 35.

11. A fiber of the aromatic-aliphatic copolyamide recited in claim 1,having a tenacity value in excess of about 4.5 g.p.d., initial modulusvalue in excess of about 400 g.p.d., and an orientation angle less thanabout 25.

12. A process for improving tensile properties of a fiber of thearomatic-aliphatic copolyamide of claim 1, comprising applying heat inthe temperature range of between about 300 to 600 C. to said fiber forbetween about 0.l to ID seconds in an inert atmosphere, while drawingsaid fiber from about 0 to 50 percent.

13. A process as recited in claim l2, wherein said temperature range isbetween about 400 to 550C.

t t i t i

2. An aromatic-aliphatic ordered copolyamide as recited in claim 1,wherein R is selected from the group consisting of hydrogen, halogen,lower alkyl, lower alkoxy, cyano, nitro, alkylthio, alkysulfonyl,alkylsulfamoyl, and carboalkoxy.
 3. An aromatic-aliphatic orderedcopolyamide as recited in claim 1, wherein the sum of X+Y is 8 and Z is4.
 4. An aromatic-aliphatic ordered copolyamide as recited in claim 1,wherein the sum of X+Y is 12 and Z is
 4. 5. An aromatic-aliphaticordered copolyamide as recited in claim 1, wherein the sum of X+Y is 23and Z is
 4. 6. An aromatic-aliphatic ordered copolyamide as recited inclaim 1, wherein the sum of X+Y is 12 and Z is
 5. 7. A shaped article ofthe aromatic-aliphatic copolyamide recited in claim
 1. 8. A shapedarticle of claim 7 in film form.
 9. A shaped article of claim 7 in fiberform.
 10. A fiber of the aromatic-aliphatic copolyamide recited in claim1, having a tenacity value in excess of about 3 g.p.d., initial modulusvalue in excess of about 275 g.p.d., and an orientation angle less thanabout 35* .
 11. A fiber of the aromatic-aliphatic copolyamide recited inclaim 1, having a tenacity value in excess of about 4.5 g.p.d., initialmodulus value in excess of about 400 g.p.d., and an orientation angleless than about 25* .
 12. A process for improving tensile properties ofa fiber of the aromatic-aliphatic copolyamide of claim 1, comprisingapplying heat in the temperature range of between about 300* to 600* C.to said fiber for between about 0.1 to 10 seconds in an inertatmosphere, while drawing said fiber from about 0 to 50 percent.
 13. Aprocess as recited in claim 12, wherein said temperature range isbetween about 400* to 550* C.